The invention relates to organic concentrates that can be diluted to form aqueous organic dispersions useful in removing polymeric films and organic soils. More particularly, the invention relates to the use of certain solvent blends for forming aqueous dispersions of water-activated materials. These dispersions are useful for removing soils and films from a variety of common substrates including fabrics, porous surfaces and hard surfaces. Further, the aqueous diluted composition can be used to remove organic soils or polymeric films from woven and non-woven fabrics and from hard surfaces such as metal surfaces, floor surfaces, wood surfaces, vinyl surfaces, etc. The aqueous organic materials of the invention are surprisingly effective in removing stubborn crosslinked resistant films or organic layers from a variety of substrates. The aqueous organic materials can be manufactured in the form of a non-aqueous concentrate and used as an aqueous dispersion after dilution.
The removal of polymeric films and organic soils from a variety of substrates has been a goal of many investigators for many years. In large part, such investigations have focused on films or soils that are formed on fabric materials such as woven and non-woven fabrics and on hard surfaces such as metal, wood, concrete, vinyl, composite, etc. These polymeric films typically include natural products such as protein and cellulosics, synthetic polymers such as linear or crosslinked acrylics, urethanes, etc. Fabrics and hard surfaces, both porous and nonporous, can be covered with materials intentionally or unintentionally contacted or applied to the locus. Intentionally applied materials include floor finishes, paints, lacquers, adhesives, graffiti, oxidized or polymerized food soils, photoresist, etc. Such materials are generally organic polymeric materials that can also be crosslinked using isocyanate, aziridine, air-oxidation, silane or epoxy chemistries. Woven and non-woven fabrics can be soiled in food processing. Fabrics can be soiled in industrial chemical processing such as in the use of photoresists (exposed and unexposed) in making printed circuit boards or integrated circuits. In large part, one important aspect of the invention is focused on the removal of such crosslinked and non-crosslinked polymeric materials from a variety of substrates in a variety of processes such as hard surface cleaning, floor stripping, laundry, etc.
Stripping compositions for removing paint, lacquer, floor finish, alkyd paints are also well known. Common strippers are commonly either aqueous alkaline solutions, aromatic hydrocarbon liquids such as xylene blends, methylene chloride (CH2Cl2) or aqueous CH2Cl2 dispersions, dispersions of fluorocarbon surfactants and a variety of other materials. These strippers are useful, but can pose operating and environmental unpleasantness, inconvenience or hazard.
Laundry cleaners are commonly manufactured by combining organic and inorganic materials to form formulations comprising detergents, builders, defoamers and a variety of other ingredients that typically modify the surface energy in the soil to promote soil release and cleaning properties. These compositions tend to be primarily directed to changing the nature of the interface environment between the soil and the fabric. Specialty laundry strippers, solvents and other systems are known in unique cleaning systems.
We have found, for example, Johnson, U.S. Pat. No. 4,592,787, which teaches a polymer stripper used in aqueous form comprising an inorganic basic material, an alkanol amine, a lower alkanol and a propylene glycol ether. Ward et al., U.S. Pat. No. 4,992,108, teach an organic polymer stripper composition comprising an aromatic hydrocarbon and an organic sulfonic acid material. The Ward et al. materials are non-aqueous strippers. Doscher, U.S. Pat. No. 5,007,969, discloses a liquid solvent comprising a low toxicity, low vapor pressure solvent based on organic carbonate compositions. Horn et al., U.S. Pat. No. 5,529,887, disclose a polymeric stripper composition based on fluorine chemistry containing an inorganic base, a water soluble fluoride composition and organic solvents. Van Eenam, U.S. Pat. Nos. 5,080,831 and 5,158,710, disclose aqueous degreaser compositions comprising a variety of organic solvents, surfactants, inorganic bases and other components. The Van Eenam materials are formulated in clear aqueous composition requiring a surfactant material that balances the nature of the solvents in the aqueous composition and also requires the presence of an inorganic base, sequestrant and inorganic builder material to enhance cleaning degreasing efficacy. Appropriate balance of materials in the Van Eenam system is indicated by a clear solution or a clear, transparent microemulsion in the presence of water. Van Eenam, U.S. Pat. No. 5,158,710, exemplifies cleaner/degreaser materials containing 1-phenoxy-2-propanol, an alcohol amine base, a silicate base and an anionic sulfonate surfactant material. These materials in admixture are critical to achieve the cleaning results required by Van Eenam. Van Eenam, WO 91/09104, published Jun. 27, 1991, exemplifies a cleaner/degreaser comprising 1-phenoxy-2-propanol combined with a fatty diethanol amide surfactant material optionally combined with a monoethanolamine aqueous base. Van Eenam also discloses the use of acrylic and other thickeners and materials that enhance viscosity and cleaning. Van Eenam, U.S. Pat. No. 5,419,848, teaches stable compositions comprising a sparingly soluble organic solvent, a thickener typically comprising a clay or a polymeric material, and an organic or inorganic base. Further, Van Eenam, U.S. Pat. No. 5,585,341, discloses similar compositions to the previous Van Eenam patent except that these materials are described as substantially non-aqueous, contain much less than 10 wt % water and include a solubilizing anionic or nonionic surfactant component such as an alkyl benzene sulfonic acid, an alcohol ethoxylate surfactant, an aliphatic phosphate ester, etc. The Van Eenam patents typically set the use level of the compositions of the invention at or below the solubility of the compositions ingredients in the aqueous media used in the Van Eenam disclosure.
Conventional concentrated, water-soluble dilutable cleaner/degreaser compositions typically comprise substantially water soluble organic solvents such as ethylene glycol monobutylether, diethylene glycol monobutylether, ethyl diethylene glycol monoethylether, other related cellosolves or carbitols, isopropyl alcohol in combination with anionic nonionic surfactants and conventional adjuvants such as chelants, builders, perfumes, dyes, pH, modifiers, etc. Typically such materials require in the following formulation motif, a builder, a base, an adjuvant such as a chelator or thickener, etc. for activity:
Other conventional cleaner/degreaser emulsion compositions are typically water-in-oil or oil-in-water emulsions in which the organic solvent is substantially water insoluble. Such emulsions can contain insoluble materials such as toluene, orthodichlorobenzene or mixtures thereof with emulsifier compositions. Other available emulsions can comprise xylene, kerosene, mineral spirits, benzene, naphthalene, sulfonates, emulsified with various surfactants to form dispersions in aqueous media. Illustrative such available compositions are marketed under the tradenames: Brulin 512(copyright), Spartan WRD-60(copyright), Betco Emulsifiable Solvent Degreaser(copyright), Amrepjel-sol(copyright) and Boisactusol(copyright). These emulsions are inherently water insoluble organic solvents, typically a hydrocarbon solvent emulsified with a surfactant coupler in the solvent component. In large part, the prior art is typically non-aqueous or uses an aqueous medium as a carrier for the active ingredients. The prior art does not recognize that water can be an active and an important ingredient in the compositions that can cooperate with the other components in achieving increased activity.
Conventional stripper formulations are water-soluble concentrates with a composition typically comprised of primarily water soluble glycol ether solvent, alkanolamine, alkali, surfactant, and water.
Even in view of the large body of prior art relating to cleaner/degreaser and stripper compositions, a substantial need exists for materials that are active in removing hard floor finishes and crosslinked finishes, photo-resist materials and contaminating polymeric material from fabrics and other substrates. A substantial need exists for low cost, highly active, easily formulated soil and polymer film removing compositions.
We have surprisingly found that blends of certain substantially water-insoluble ether alcohol solvent materials with a solvent coupler results in a concentrate that can be mixed with water to make an improved dispersion useful in soil removal. The ether alcohol, having relatively low water solubility and relatively low volatility, in an aqueous medium exhibits surprisingly enhanced soil or film removing properties when combined with the solvent coupler. This is particularly surprising in that the system is most effective when the solvent coupler level is such that it is insufficient to solubilize the water-insoluble ether alcohol solvent into aqueous solution, forming a composition in the form of a dispersion. We have found that the nature of the material when diluted in water must be a dispersion of the material in the aqueous medium. The solubility of the total organic part must be such that at least some of the organic part forms a dispersion, not a solution, of the organic material in water. We have found that the primary solvent ether alcohol material of the invention has a water solubility less than 5%, preferably less than 3%, most preferably less than 2% in water. The solvents and solvent coupler compositions of the invention are also of reduced volatility. The vapor pressure of the neat liquids is independently less than 1 mm-Hg, preferably less than 0.8 mm-Hg, with a flash point of greater than 90xc2x0 C., preferably greater than 100xc2x0 C.
The preferred primary solvent in the invention comprises a phenyl ether typically an ethylene glycol phenyl ether or propylene glycol phenyl ether. The primary solvent typically has a water solubility substantially less than the first solvent/coupler material. The combined material forms the organic phase of the dispersion. A preferred blend of organic materials can be used in forming the dispersions of the invention in which a primary solvent is combined with a first solvent/coupler and a second solvent/coupler. The water solubility of these materials in order are as follows. The solubility of the first solvent/coupler is greater than the water solubility of the second solvent coupler and the solubility of the second solvent/coupler is greater than the solubility of the primary solvent material. The following table sets forth the solubilities of the useful materials in the organic phase of the dispersions.
An amount of the combined primary solvent and solvent/coupler materials is used such that the amount of organic materials added to the aqueous system is greater than the solubility of the materials in the aqueous system. In other words, by example, if a combined solvent, solvent/coupler material is added to an aqueous medium in an amount of about 10 wt % or more of the aqueous medium, the solubility of the organic phase is less than 10 wt %, preferably less than 2 wt %.
We have found a preferred primary solvent system. The solvent materials comprise an ethylene glycol or propylene glycol phenyl ether solvent composition of the formula:
HOxe2x80x94R1xe2x80x94Oxe2x80x94PH
wherein R1 is a C2-3 alkylene group and PH represents an aromatic ring such as phenyl, substituted phenyl, naphthyl, etc. This primary solvent can be made to cooperate with an ether alcohol coupler/solvent composition and in an aqueous medium to form a highly effective stripper cleaner composition in the form of an aqueous dispersion. We have found that these materials, at the right concentrations, cooperate to obtain polymer removal of difficult to remove materials such as highly crosslinked hard urethane and acrylic floor finishes. Such films were previously resistant to solvent-based removal methods. We have found that water is an essential ingredient and serves to activate the alkylene glycol phenyl ether mixture with the alcohol ether coupler solvent. We have also found that the selection of the amounts of the alkylene glycol phenyl ether, the ether alcohol coupler/cosolvent, the relative proportions of the solvent and the coupler and the nature of the composition comprising the coupler/solvent in an aqueous dispersion is important. The dilute materials have optimum activity when dispersed in an aqueous medium and are visibly hazy, cloudy or opaque. The solubility of the combined solvent and solvent/coupler composition is above combined solubility limits. The aqueous materials of the invention comprise an ethylene glycol or propylene glycol phenyl ether solvent composition combined with an ether alcohol coupler/solvent composition, with the phenyl ether solvent having the following structure:
HOxe2x80x94R1xe2x80x94Oxe2x80x94PH
wherein R1 is a C2-3 alkylene group and PH represents an aromatic ring such as phenyl. The preferred phenyl ether primary solvents have a water solubility of about 1 wt %.
We have also found a preferred ether alcohol coupler solvent that comprises a blend of a first alcohol ether coupler/solvent having the formula:
R2xe2x80x94Oxe2x80x94(R3O)mH
wherein R2 is a C2-10 linear or branched alkyl, preferably a C2-5 alkyl, R3 comprises a C2-10 alkylene, preferably a C2-3 alkylene and m is 1 to 6, preferably 1 or 2. Preferably, R2 comprises ethyl, propyl, isopropyl, butyl or t-butyl and R3 comprises ethylene or propylene and a second alcohol ether coupler/solvent having the formula:
xe2x80x83R4xe2x80x94Oxe2x80x94(R5O)mH
R4 is C2-10 linear or branched alkyl, R5 comprises a C2-10 alkylene and m is 1 to 6. Preferably, the ether alcohol coupler/solvent comprises:
R4xe2x80x94Oxe2x80x94(R5O)mH
wherein R4 comprises a C2-10 linear or branched alkyl group, R5 comprises an ethylene, or propylene moiety, m is a number from 1 to 3. The solubility of the combination of the primary solvent with either the single part solvent coupler or the two part solvent coupler is less than about 5 grams of solvent per 100 grams of water. Other preferred blends of primary solvent and solvent/couplers have a flash point greater than about 90xc2x0 C., typically greater than about 100xc2x0 C. The vapor pressure of the preferred materials is less than about 0.1 millimeter of mercury, typically less than about 0.08 millimeter of mercury (mm-Hg).
We believe that the solvent material comprising an alkylene glycol phenyl ether is a primary film removing agent. The alcohol ether solvent coupler provides both removal properties and couples the alkylene glycol phenyl ether into an effective aqueous dispersion or emulsion. We have found that water is an essential component to the ingredient. Using the alkylene glycol phenyl ether and the coupler solvent at claimed proportions in an aqueous dispersion or emulsion results in an organic film removing composition that is substantially more active than the non-aqueous material or related formulations. Further, the use of a blended solvent coupler in the aqueous media still further enhance film removal properties. For the purpose of this patent application, the useful materials can be free of any one of an organic base, a nitrogen base, a solubilizing anionic surfactant additive, a fluorocarbon material, a fluorocarbon surfactant and polymeric or clay thickeners. We have found that the materials are used at a concentration that is approximately equal to or exceeds the aqueous solubility of the combined solvent and alcohol ether coupler/solvent materials combined. The resulting materials have the appearance of a hazy or cloudy liquid or an opaque white dispersion. For the purpose of this patent applications, the proportions of primary solvent to coupler solvent to water are such that a dispersion or emulsion is formed rather than a clear solution.
We have found that the stability of the dispersion and certain soil removal properties can be enhanced by the use of an effective amount of an nonionic ether surfactant material such as an EOPO block copolymer or an alcohol ethoxylate material. The materials of the invention find substantially improved soil removal properties without using aromatic solvents, chlorinated or fluorinated materials, polymeric or inorganic thickener materials and rely substantially on the solvent materials. These compositions can be removed by rinsing, vacuuming, mopping or by simply exposing the clean surface to the ambient atmosphere for drying at ambient or slightly elevated temperatures.
Further, antimicrobial agents or biocides, well-known to the art, can be incorporated into the compositions for microbial control. Biocides are antimicrobial agents or chemical compositions that can prevent microbiological contamination or deterioration caused by microorganisms. Most useful antimicrobial agents comprise phenolics, halogen compounds, quaternary ammonium compounds, amines, alkanol amines, nitro compounds and a variety of miscellaneous types of antimicrobial agents. Antimicrobial agents operate by either interfering with a cellular mechanism or a cellular component of the microbe resulting in the substantial reduction of microbial populations or simply prevent proliferation in numbers of microorganisms that would prevent the accumulation of harmful numbers of microorganisms. Antimicrobial agents are often effective against one or more of typical microbial classifications such as gram positive, gram negative, fungi, molds and yeasts. The preferred antimicrobial agent used to kill or reduce microbial populations requires physical and chemical compatibility with the system, stability and resistance to be inactivated by other components or ingredients in this system, stability under use and storage conditions of pH temperature and light exposure while being safe and essentially non-toxic to humans in handling formulation and use. Typical antimicrobial agents are used in aqueous systems solution at a concentration of about 0. 1 to 10,000 ppm. The preferred agents can include cationic species including but not limited to quaternary ammonium compounds, chlorhexidine gluconate, amine salts; phenolic derivatives such as tert-amylphenol, chlorobenzylphenol, benzylphenol, p-chloro-meta-xylenol; 5-chloro-2-(2,4-dichlorophenoxy)phenol (triclosan); hydrogen peroxide; peracids; organic peroxides; and fatty acids.
We have also found extremely effective methods for removing generic coatings from a variety of fabric or hard surfaces. We have found that even highly crosslinked urethane finishes, crosslinked and uncrosslinked acrylic finishes and other common polymeric materials are easily and rapidly removed using the compositions of the invention.
The invention relies in compositions and methods of using the compositions in removing organic films and soils. In one aspect of the invention, the invention resides in a concentrate material that comprises a blend of the solvent and ether alcohol solvent couplers in the substantial absence of water. Such concentrate materials can be used in inventive methods in which the concentrates are combined with water to form an active dispersion or emulsion. These dispersions or emulsions can be used in methods of removing the organic films or soils. Further, the invention resides in aqueous use solutions comprising the solvent combined with the ether alcohol solvents of the invention to form a highly effective composition that can be used to remove organic soils or films. Such materials are also applicable in inventive methods disclosed in the application.
The primary solvent material used in the compositions of the invention comprise the composition of the formula:
HOxe2x80x94R1xe2x80x94Oxe2x80x94PH
wherein R1 comprises a C2-3 alkylene group and PH represents an aromatic monocyclic ring, the solvent having a solubility of less than 5 grams of solvent per 100 grams of water or aqueous medium. Preferred primary solvents for use in this invention comprise an ethylene glycol phenyl ether or a propylene glycol phenyl ether composition. While the diethylene glycol phenyl ether and the dipropylene glycol phenyl ether have some activity in this application, ethylene glycol, propylene glycol phenyl ether or mixtures thereof are preferred. Further, the use of other aromatic nuclei other than phenyl also tends to reduce activity.
We have found that the primary solvent material is coupled into the aqueous dispersion or emulsion using an ether alcohol solvent coupler composition. This coupler composition has a solubility greater than the solubility of the primary solvent, and is substantially soluble in water or the aqueous medium. We believe that the solubility limitations are important indicia of active solvent materials. The ether alcohol solvent coupler comprises a compound of the formula:
R2xe2x80x94Oxe2x80x94(R3O)mH
wherein R2 comprises a C2-10 linear or branched alkyl group and R3 comprises a C2-10 alkylene group and m is a number of 1 to 6.
A preferred solvent coupler comprises a blend of a first solvent coupler comprising the formula:
R2xe2x80x94Oxe2x80x94(R3O)mxe2x80x94OH
wherein R2 is a C2-4 alkyl, R3 is ethylene or propylene and m is 1 or 2. A second solvent coupler comprises the formula:
R4xe2x80x94Oxe2x80x94(R5O)nxe2x80x94OH
wherein R4 comprises a C2-4 alkyl group, R5 comprises ethylene or propylene and n is 1 or 2. These solvent/coupler materials have a water solubility greater than the primary solvent.
Formulations useful in the invention can be exemplified by the following formulation tables:
The improved cleaning efficiency of the compositions of the invention rely on the use of a primary solvent comprising 2-phenoxy propanol or 2-phenoxy ethanol. This water-insoluble aromatic ether solvent appears to be an excellent solvent cleaner material. The aromatic ether solvent material of the invention requires an ether alcohol coupler material having aqueous solubility greater than the aromatic ether solvent that provides solvent properties that enhance the film removing properties of the invention, but also aid in coupling the aromatic ether alcohol solvent into aqueous dispersion.
Examples of lower alkyl ethers of ethylene or propylene glycol useful in this invention include ethylene glycol ethyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol isopropyl ether, propylene glycol butyl ether, propylene glycol isobutyl ether, propylene glycol tertiary butyl ether. The preferred solvent/coupler comprises ethylene or propylene glycol butyl ether. Further, the stability and activity of the compositions of the invention can be enhanced by the presence of a second solvent/coupler material. Examples of the second solvent/coupler material of the invention include diethylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol isopropyl ether, dipropylene glycol butyl ether, dipropylene glycol isobutyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, tripropylene glycol propyl ether, tripropylene glycol isopropyl ether, tripropylene glycol butyl ether and tripropylene glycol isobutyl ether.
The cleaning capacity, product uniformity and other utility of the compositions of the invention can be improved by the presence of a surfactant material. Preferably the surfactant is nonionic in nature. Preferred nonionic surfactants for use in the invention can include any nonionic surfactant having a region of relative hydrophobicity and a region of hydrophilicity. Typically, regions of hydrophilicity comprise a polymeric block of ethylene oxide, typically greater than 3 moles of ethylene oxide, preferably 5 to 20 moles of ethylene oxide. The regions of relative hydrophobicity can be manufactured from linear alcohols, alkyl phenyl groups, blocks of polymerized propylene oxide or other relatively hydrophobic compositions. Preferred nonionic surfactants for use in this invention include alcohol ethoxylates and surfactant compositions comprising at least an ethylene oxide block (EO)x and a propylene oxide block (PO)y wherein EO represents ethylene oxide and PO represents propylene oxide while x represents 3 to 16 and y represents 3 to 16. Most preferred surfactants of the invention comprise alcohol ethoxylates made by reacting an alcohol or alkylphenol or sodium alkoxylate salts thereof with 3 to 16 moles of ethylene oxide to form the alcohol ethoxylate surfactant. Preferred alcohols for use in the invention are typical fatty alcohols having linear fatty groups with 9 to 24 carbon atoms, preferably 9 to 16 carbon atoms. The aqueous concentrates and dispersions of the organic phase in the aqueous media can also contain the presence of additive materials. Such additives include dyes, perfumes, alkalinity sources such as ammonia, alkanol amines, caustic materials, fluorescing agents, biocidal agents, etc.